Balancing volumetric and gravimetric uptake in highly porous materials for clean energy

A huge challenge facing scientists is the development of adsorbent materials that exhibit ultrahigh porosity but maintain balance between gravimetric and volumetric surface areas for the onboard storage of hydrogen and methane gas—alternatives to conventional fossil fuels. Here we report the simulation-motivated synthesis of ultraporous metal–organic frameworks (MOFs) based on metal trinuclear clusters, namely, NU-1501-M (M = Al or Fe). Relative to other ultraporous MOFs, NU-1501-Al exhibits concurrently a high gravimetric Brunauer−Emmett−Teller (BET) area of 7310 m2 g−1 and a volumetric BET area of 2060 m2 cm−3 while satisfying the four BET consistency criteria. The high porosity and surface area of this MOF yielded impressive gravimetric and volumetric storage performances for hydrogen and methane: NU-1501-Al surpasses the gravimetric methane storage U.S. Department of Energy target (0.5 g g−1) with an uptake of 0.66 g g−1 [262 cm3 (standard temperature and pressure, STP) cm−3] at 100 bar/270 K and a 5- to 100-bar working capacity of 0.60 g g−1 [238 cm3 (STP) cm−3] at 270 K; it also shows one of the best deliverable hydrogen capacities (14.0 weight %, 46.2 g liter−1) under a combined temperature and pressure swing (77 K/100 bar → 160 K/5 bar).

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Synthetic models of hydrogenases based on framework structures containing coordinating P, N-atoms as hydrogen energy electrocatalysts – from molecules to materials

Pure and Applied Chemistry ◽

10.1515/pac-2019-1207 ◽

2020 ◽

Vol 92 (8) ◽

pp. 1305-1320 ◽

Cited By ~ 1

Author(s):

Yulia H. Budnikova ◽

Vera V. Khrizanforova

Keyword(s):

Fossil Fuels ◽

High Current Density ◽

Clean Energy ◽

Hydrogen Energy ◽

Energy Technologies ◽

Highly Active ◽

Synthetic Materials ◽

Metal Derivatives ◽

Metal Organic ◽

Metal Doped

AbstractNowadays, hydrogen has become not only an extremely important chemical product but also a promising clean energy carrier for replacing fossil fuels. Production of molecular H2 through electrochemical hydrogen evolution reactions is crucial for the development of clean-energy technologies. The development of economically viable and efficient H2 production/oxidation catalysts is a key step in the creation of H2-based renewable energy infrastructure. Intrinsic limitations of both natural enzymes and synthetic materials have led researchers to explore enzyme-induced catalysts to realize a high current density at a low overpotential. In recent times, highly active widespread numerous electrocatalysts, both homogeneous or heterogeneous (immobilized on the electrode), such as transition metal complexes, heteroatom- or metal-doped nanocarbons, metal-organic frameworks, and other metal derivatives (calix [4] resorcinols, pectates, etc.), which are, to one extent or another, structural or functional analogs of hydrogenases, have been extensively studied as alternatives for Pt-based catalysts, demonstrating prospects for the development of a “hydrogen economy”. This mini-review generalizes some achievements in the field of development of new electrocatalysts for H2 production/oxidation and their application for fuel cells, mainly focuses on the consideration of the catalytic activity of M[P2N2]22+ (M = Ni, Fe) complexes and other nickel structures which have been recently obtained.

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Benchmark Study of Hydrogen Storage in Metal–Organic Frameworks under Temperature and Pressure Swing Conditions

ACS Energy Letters ◽

10.1021/acsenergylett.8b00154 ◽

2018 ◽

Vol 3 (3) ◽

pp. 748-754 ◽

Cited By ~ 71

Author(s):

Paula García-Holley ◽

Benjamin Schweitzer ◽

Timur Islamoglu ◽

Yangyang Liu ◽

Lu Lin ◽

...

Keyword(s):

Hydrogen Storage ◽

Metal Organic Frameworks ◽

Benchmark Study ◽

Metal Organic ◽

Temperature And Pressure ◽

Pressure Swing

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Reticular Chemistry and Metal-Organic Frameworks for Clean Energy

MRS Bulletin ◽

10.1557/mrs2009.180 ◽

2009 ◽

Vol 34 (9) ◽

pp. 682-690 ◽

Cited By ~ 64

Author(s):

Omar M. Yaghi ◽

Qiaowei Li

Keyword(s):

Carbon Dioxide ◽

Metal Organic Frameworks ◽

Clean Energy ◽

Building Blocks ◽

Zeolitic Imidazolate Frameworks ◽

Design Concepts ◽

Surface Areas ◽

Molecular Building Blocks ◽

Metal Organic ◽

Molecular Aspects

AbstractReticular chemistry concerns the linking of molecular building blocks into predetermined structures using strong bonds. We have been working on creating and developing the conceptual and practical basis of this new area of research. As a result, new classes of crystalline porous materials have been designed and synthesized: metal-organic frameworks, zeolitic imidazolate frameworks, and covalent organic frameworks. Crystals of this type have exceptional surface areas (2,000−6,000 m2/g) and take up voluminous amounts of hydrogen (7.5 wt% at 77 K and 3−4 × 106 Pa), methane (50 wt% at 298 K and 2.5 × 106 Pa), and carbon dioxide (140 wt% at 298 K and 3 × 106 Pa). We have driven the basic science all the way to applications without losing sight of our quest for understanding the underlying molecular aspects of this chemistry. The presentation was focused on the design concepts, synthesis, and structure of these materials, with emphasis on their applications to onboard energy storage.

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Implementing Metal-Organic Frameworks for Natural Gas Storage

Crystals ◽

10.3390/cryst9080406 ◽

2019 ◽

Vol 9 (8) ◽

pp. 406 ◽

Cited By ~ 5

Author(s):

Eyas Mahmoud ◽

Labeeb Ali ◽

Asmaa El Sayah ◽

Sara Awni Alkhatib ◽

Hend Abdulsalam ◽

...

Keyword(s):

Natural Gas ◽

Thermal Management ◽

Active Sites ◽

Storage Capacity ◽

Metal Organic Frameworks ◽

Department Of Energy ◽

Working Capacity ◽

Adsorbed Natural Gas ◽

Metal Organic ◽

Temperature And Pressure

Methane can be stored by metal-organic frameworks (MOFs). However, there remain challenges in the implementation of MOFs for adsorbed natural gas (ANG) systems. These challenges include thermal management, storage capacity losses due to MOF packing and densification, and natural gas impurities. In this review, we discuss discoveries about how MOFs can be designed to address these three challenges. For example, Fe(bdp) (bdp2− = 1,4-benzenedipyrazolate) was discovered to have intrinsic thermal management and released 41% less heat than HKUST-1 (HKUST = Hong Kong University of Science and Technology) during adsorption. Monolithic HKUST-1 was discovered to have a working capacity 259 cm3 (STP) cm−3 (STP = standard temperature and pressure equivalent volume of methane per volume of the adsorbent material: T = 273.15 K, P = 101.325 kPa), which is a 50% improvement over any other previously reported experimental value and virtually matches the 2012 Department of Energy (Department of Energy = DOE) target of 263 cm3 (STP) cm−3 after successful packing and densification. In the case of natural gas impurities, higher hydrocarbons and other molecules may poison or block active sites in MOFs, resulting in up to a 50% reduction of the deliverable energy. This reduction can be mitigated by pore engineering.

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Đánh giá khả năng hấp phụ khí H2 và CO2 trong MIL-88A-Fe bằng phương pháp mô phỏng Monte Carlo chính tắc lớn

Journal of Science, Quy Nhon University ◽

10.52111/qnjs.2021.15101 ◽

2021 ◽

Vol 15 (1) ◽

pp. 5-12

Author(s):

Huynh Nguyen ◽

Keyword(s):

Monte Carlo ◽

Environmental Pollution ◽

Co2 Capture ◽

Electrostatic Interactions ◽

Fossil Fuels ◽

Clean Energy ◽

High Porosity ◽

Global Issues ◽

Metal Framework ◽

Carbon Dioxide Co2

Two of the global issues are finding new, clean energy sources to replace increasingly exhausting fossil fuels and overcome the problem of environmental pollution and climate change. In recent years, organic-metal framework series has been considered as a great candidate for H¬2 storage and CO2 capture to provide clean energy and reduce environmental pollution. Among them, MIL-88A-Fe has a stable and flexible structure in moist environments and high porosity. Therefore, in this research, hydrogen (H2) storage and carbon dioxide (CO2) capture capacities in MIL-88A-Fe were assessed quantitatively. By the grand canonical Monte Carlo simulation, the adsorption capacities of MIL-88A were elucidated via the adsorption isotherms, heats of adsorption at finite temperatures of 77 K and 298 K and pressures up to 100 bar. The results show that parameterizing force fields by combining DDEC method to calculate atomic partial charges for electrostatic interactions and the universal force field parameters for the Lennard-Jones interactions provide a quick and reliable method to evaluate gas capture and storage capacities of porous materials. The results also indicate that the abilities of H2 storage and CO2 capture of MIL-88A-Fe in gravimetric capacities were not very high; however, they were noticeable in volumetric uptakes. The hydrogen molecule is strongly adsorbed in the hollow positions of O and Fe atoms, while the CO2 molecule is more evenly distributed in the sorbent.

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Metal Organic Frameworks Based Materials for Heterogeneous Photocatalysis

Molecules ◽

10.3390/molecules23112947 ◽

2018 ◽

Vol 23 (11) ◽

pp. 2947 ◽

Cited By ~ 23

Author(s):

Shu-Na Zhao ◽

Guangbo Wang ◽

Dirk Poelman ◽

Pascal Van Der Voort

Keyword(s):

Fossil Fuels ◽

Sustainable Energy ◽

Metal Organic Frameworks ◽

Co2 Reduction ◽

Clean Energy ◽

Heterogeneous Photocatalysis ◽

Chemical Systems ◽

Challenges And Opportunities ◽

Metal Organic ◽

Clean Energy Source

The increase in environmental pollution due to the excessive use of fossil fuels has prompted the development of alternative and sustainable energy sources. As an abundant and sustainable energy, solar energy represents the most attractive and promising clean energy source for replacing fossil fuels. Metal organic frameworks (MOFs) are easily constructed and can be tailored towards favorable photocatalytic properties in pollution degradation, organic transformations, CO2 reduction and water splitting. In this review, we first summarize the different roles of MOF materials in the photoredox chemical systems. Then, the typical applications of MOF materials in heterogeneous photocatalysis are discussed in detail. Finally, the challenges and opportunities in this promising field are evaluated.

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A Process for Carbon Dioxide Capture Using Schiff Bases Containing a Trimethoprim Unit

Processes ◽

10.3390/pr9040707 ◽

2021 ◽

Vol 9 (4) ◽

pp. 707

Author(s):

Anaheed A. Yaseen ◽

Emaad T. B. Al-Tikrity ◽

Gamal A. El-Hiti ◽

Dina S. Ahmed ◽

Mohammed A. Baashen ◽

...

Keyword(s):

Carbon Dioxide ◽

Schiff Bases ◽

Fossil Fuels ◽

Carbon Dioxide Capture ◽

Aromatic Aldehydes ◽

Average Pore ◽

Research Attention ◽

Carbon Dioxide Uptake ◽

Surface Areas ◽

Temperature And Pressure

Environmental problems associated with the growing levels of carbon dioxide in the atmosphere due to the burning of fossil fuels to satisfy the high demand for energy are a pressing concern. Therefore, the design of new materials for carbon dioxide storage has received increasing research attention. In this work, we report the synthesis of three new Schiff bases containing a trimethoprim unit and the investigation of their application as adsorbents for carbon dioxide capture. The reaction of trimethoprim and aromatic aldehydes in acid medium gave the corresponding Schiff bases in 83%–87% yields. The Schiff bases exhibited surface areas ranging from 4.15 to 20.33 m2/g, pore volumes of 0.0036–0.0086 cm3/g, and average pore diameters of 6.64–1.4 nm. An excellent carbon dioxide uptake (27–46 wt%) was achieved at high temperature and pressure (313 K and 40 bar, respectively) using the Schiff bases. The 3-hydroxyphenyl-substituted Schiff base, which exhibited a meta-arrangement, provided the highest carbon dioxide uptake (46 wt%) due to its higher surface area, pore volume, and pore diameter compared with the other two derivatives with a para-arrangement.

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A Systematic Study on Bio-Based Hybrid Aerogels Made of Tannin and Silica

Materials ◽

10.3390/ma14185231 ◽

2021 ◽

Vol 14 (18) ◽

pp. 5231

Author(s):

Ann-Kathrin Koopmann ◽

Wim J. Malfait ◽

Thomas Sepperer ◽

Nicola Huesing

Keyword(s):

Specific Surface ◽

Processing Parameters ◽

Water Soluble ◽

High Porosity ◽

Mesopore Volume ◽

One Pot ◽

Surface Areas ◽

Hybrid Aerogels ◽

Highly Porous ◽

Silica Hybrid

Tannin-silica hybrid materials are expected to feature excellent mechanic-chemical stability, large surface areas, high porosity and possess, after carbothermal reduction, high thermal stability as well as high thermal conductivity. Typically, a commercially available tetraethoxysilane is used, but in this study, a more sustainable route was developed by using a glycol-based silica precursor, tetrakis(2-hydroxyethyl)orthosilicate (EGMS), which is highly water-soluble. In order to produce highly porous, homogeneous hybrid tannin-silica aerogels in a one-pot approach, a suitable crosslinker has to be used. It was found that an aldehyde-functionalized silane (triethoxysilylbutyraldehyde) enables the covalent bonding of tannin and silica. Solely by altering the processing parameters, distinctly different tannin-silica hybrid material properties could be achieved. In particular, the amount of crosslinker is a significant factor with respect to altering the materials’ properties, e.g., the specific surface area. Notably, 5 wt% of crosslinker presents an optimal percentage to obtain a sustainable tannin-silica hybrid system with high specific surface areas of roughly 800–900 m2 g−1 as well as a high mesopore volume. The synthesized tannin-silica hybrid aerogels permit the usage as green precursor for silicon carbide materials.

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One-Pot, Room-Temperature Conversion of CO2 into Porous Metal−Organic Frameworks

10.26434/chemrxiv.13363694 ◽

2020 ◽

Author(s):

Kentaro Kadota ◽

You-Lee Hong ◽

Yusuke Nishiyama ◽

Easan Sivaniah ◽

Daniel Packwood ◽

...

Keyword(s):

Atmospheric Pressure ◽

Metal Organic Frameworks ◽

Porous Metal ◽

One Pot ◽

Surface Areas ◽

Piperazine Derivatives ◽

Metal Organic ◽

The One ◽

Crystalline Metal ◽

Highly Porous

We demonstrate the one-pot synthesis of highly porous crystalline metal−organic frameworks, [Zn4O(piperazine dicarbamate)3], an analogue of [Zn4O(1,4-benzenedicarboxylate)3] (MOF-5), directly from atmospheric pressure CO2 gas and piperazine derivatives at 25 °C. The structures showed high CO2 contents over 30 wt% and surface areas of 1270−2366 m2 g−1. We also show that the synthesis is feasible even by the use of 400 ppm of CO2.

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Machine Learning-Guided Equations for Super-Fast Prediction of Methane Storage Capacities of COFs

10.26434/chemrxiv.13469787 ◽

2020 ◽

Author(s):

Alauddin Ahmed

Keyword(s):

High Capacity ◽

Nanoporous Materials ◽

Department Of Energy ◽

Percentage Error ◽

Methane Storage ◽

On Demand ◽

Temperature And Pressure ◽

Pressure Swing ◽

Fast Prediction ◽

Methane Capacity

Covalent organic framework (COF) is a prominent class of nanoporous materials under consideration for vehicular methane storage. However, evaluating a COF for its methane capacity involves multiple experimental or computational steps, which is expensive and time consuming. Consequently, the discovery of high-capacity COFs for methane storage is very slow. Here we developed equations for super-fast prediction of deliverable methane capacities of COFs from a small number (3 to 7) of physically meaningful and measurable crystallographic features. We provided a set of equations with different fidelities for on-demand predictions based on the accessibility of crystallographic features. We found that an equation with only three crystallographic primary features, as variables, can predict deliverable capacities of 84,800 COFs with a root-mean-square error (RMSE) of 10 cm3 (standard temperature and pressure, STP) cm-3 and mean absolute percentage error (MAPE) of 5%. However, the highest fidelity equation developed here contains seven crystallographic primary features of COFs with RMSE and MAPE of 8.1 cm3 (STP) cm-3 and 4.2%, respectively. With that, we predicted methane storage capacities of 468,343 previously unexplored COFs using the highest fidelity equation and identified several hundred promising candidates with record-setting performance. CUBE_PBB_BA2, a hypothetical COF not yet synthesized, sets the new record of balancing gravimetric (0.396 g g-1) and volumetric (221 cm3 (STP) cm-3) deliverable methane storage capacities under the pressure swing between 65 and 5.8 bar at 298K. Also, 3D-HNU5, a previously synthesized COF, has shown the potential to achieve the gravimetric and volumetric methane storage U.S. Department of Energy target (0.5 g g-1 and 315 cm3 (STP) cm-3) simultaneously with uptakes of 0.755 g g-1 and 334 cm3 (STP) cm-3 at 100 bar/270 K.

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